Manufacture of selenium oxychlorid



VICTOR LEN'HER, OF MADISON, WISCONSIN.

MANUFACTURE OF SELENIUM OXYCHLORID.

It'o Drawing.

To all whom it may concern:

Be it known that I, Vroron LENHER, a citizen of the United States,residing at Madison, in the county of Dane and State of Wisconsin, haveinvented a new and useful Improvement in the Manufacture of Selenium()xychlorid, of which the following is a s ecitication.

his invention relates to a method of manuufacturing selenium oxychlorid(seoou and the primary object is to provide a practical method ofmanufacture which will en-- able this compound to be produced on acommercial scale. s

I have discovered a practicable process of producing seleniumoxychlorid' on a commercial scale, and, having produced the compound inconsiderable quantities, I have demonstrated that it possesses suchremarkable properties as a solvent that it may be put to many usefulapplications. It may be used as a solvent for numerous substances orcompounds for which no known solvent exists, and it may be mixedorcompounded with other active compounds having the ef fect of increasingits range as a solvent, thus rendering it possible to dissolve readilysubstances or compounds which selenium oxychlorid alone will notdissolve or will dissolve onlywith difliculty. Uses for the new compoundtoo numerous to mention are contemplated by'me. Novel methods ofproducing or recovering certain substances, involving the use ofselenium oxychlorid or compounds thereof are contemplated by me. Varioususes may be made of the compound, some of which will be hereaftersuggested.

In accordance with the preferred method, I combine selenium tetrachlorid(SM 1],), which is a white crystalline solid, directly with seleniumdioxid (Se(),), which is a white crystalline solid, in such manner as toproduce selenium oxychlorid (ScOCh) di rectly in the form of a liquid,the reaction being carried on in the presence ofthe selenium oxychloridas it is progressively formed. The product, as it forms, acts as asolvent for both of the constituent compounds and this doubtlessfacilitates the reaction. It is possible also that the fresh characterof the selenium oxychlorid as it is formed may favorably influence thereaction. One may, however, after having first obtained a supply of theproduct, employ a suitable amount of the same at the outset as a solventfor the constituent compounds em- Specification of Letters Patent.

Patented June 28, 1921.

Application filed may 15, 1920. Serial No. 381,628.

ployed to produce the product, so as to have present at all stages ofthe process a solvent for the constituent compounds entering into thereaction.

e() and Sec], will combine chemically at ordinary temperatures. t ispreferred, however, to expedite the reaction by applymg a moderatedegree of heat, such as will not vaporize either of the constituentcompounds. It is preferred, also, to carry on the reaction in thepresence of a solvent for chlorin, for selenium monochlorid (Se ()l.,),and for selenium oxychlorid, such as carbon tetrachlorid (C01,),chloroform (61101,), or other suitable solvent. i

I have found it desirable, by certain novel steps'of procedure, toproduce SeCl, in suspension and then mix therewith the appropriateamount of Se(). whereupon the reaction takes place at ordinarytemperatures or may be facilitated by warming, thus carrymg on thereaction in the bath and forming tieOCl as a liquid, which dissolves inthe solvent. The solvent employed, such as C(Jh, may then be distilledover and recovered for future use, and the SeOCl will remain as aliquid. If desired, this liquid may be distilled and the vaporscondensed, thus effecting purification of the product. This may bedesirable, especially where the constituent compounds of seleniumemployed in the process, or one of them, carries impurities. A

practicable and desirable method, in accordance with the foregoing, isas follows: Mix a quantity -of-sclenium (Se), pure or impure, withcarbon tetrachlorid, or other solvent of the character mentioned above,and pass chlorin gas through the mixture, which is preferably agitatedto keep the selenium insuspcnsion, although the bubbling of the chloringas may suiiice to effect the agitation. This converts selenium intoselenium monochlorid (Se,()l,), which, as it is formed, acts as asolvent for the selenium and also dissolves in the carbon tetrachlorid.The chlorinatiml process is continued until the selenium is convertedinto Se C/l and finally into ScCl, which remains mainly in suspension inthe carbon ti-itrachlorid, although a smallamount passes into solution.Now introducc selenium dioxid ($00,) into the carbon tetrachlorid whichholds the SoUl, in suspension, and thus effect the reaction which formsthe SeOCl as a liquid, which dissolves in the carbon tetrachlorid. Heatmay he applied to facilitate the reaction.

The process should be carried out in a vessel which will not he attackedby the product, such as a porcelain. terra cotta, or glass Vessel, or aglass-lined still. An open flask may serve for the practice of theprocess on a small scale. If desired, the process may be practised bymeans of a still having facilities for applying moderate heat until theproduct is formed and tlien applying 'greater heat to distil over thecarbon tetrachlorid. and finally applying still greater heat to distilover the selenium oxychlorid. which may be recovered by a suitablecondenser. Separate eduction pipes for the distillates. provided withstop-cocks. may be a part of the equipment of the still. Also. suitableprovision should be made for discharging or cleansing from the still anyresidue of impurities which may remain in the still after theevaporation of the selenium oxychlorid.

Selenium is a solid at ordinary temperatures and may be either granularor vitreous. It may possess different forms. and may be available inmasses containing various impurities. Crude selenium may be employed inthe process or compounds of selenium may be employed. For instance,metallic compounds, such as Febe or case. may be employed as a sourcefor the' selenium, and these may be converted into Se. ,Cl inaccordance, for example, with the formula:

The Se CI may then be converted. by chlorination, to Sem If desired.SeCh may be produced by direct chlorination of selenium by passingchlorin gas over selenium.

The reactions by which the SeOCl is produced may be as follows:

The last equation indicates the proportions of the constituent compoundsto he used. This equation is satisfied by substantially twice as muchSeCh as SeO by yveight, but in practice it is preferable to emiloyslightly more than one-third of Se Selenium oxychlorid. at. normaltemperature, is a liquid of slightly yellowish cast. It boils at 176 F.and possesses a specific gravity of 2.44. It possesses remarkablesolvent qualities. being capable of dissolving many substances orcompounds for which no known solvent has hitherto existed. It is asolvent for (among others) the following substances:

Japans, paints, varnishes. rubber. pure or vulcanized;

Resins, pitch, glues, shellacs;

Lacquers, waxes, oils;

als:

Salts. certain oxids, phenolic condensation products, including theinfusible and so-cailed insoluble products, etc.

The foregoing is sufficient to show the possibilities of many diflerentapplications of selenium oxychlorid, such as the separation ofsubstances by novel processes. the production of new compounds, and theproduction of known. compounds by novel processes.

The. production of a novel compound whichwill act as a solvent forcertain substances or compounds for which the selenium oxychlorid itselfwill not serve has.

been mentioned. As an illustration. SeOCl may be used to dissolve suchactive compounds as sulfur trioxid (S0 thus producing a new compoundwhich will serve as asolvent for other substances not attacked bv knownsolvents and not attacked by 89001 itself. Again, such compoundingproduces a more active solvent for some purposes. 1'. 0., a solventwhich will act more quickly than SeOCl alone. The proportions may varywithin quite wide range. As an example. an excellent solvent'is producedby dissolving 10 parts by wei ht of SO, in

90 parts by weight of SeOC This produces a compound which will act as asolvent for arious materials. including certain oxids. for example.titanium oxid ('lifi wanadium oxid (V 0 and cohunbium pentoxid 0 Thisindicates the separation of metals from ores by newyprocesses.

A modified method of producing SeOCl in liquid form is to mix togetherselenium and water and pass chlorin gas through the mixture. applyingmoderate heat. if desired. to expeditethe reaction. The reaction may beeffected in accordance with either of the following equations:

which remains mainly in suspension in the carbon tetrachlorid. The watermay then be. intrmluced, in proper proportion. to effect the reactionindicated in the last formula,

after which the hydrochloric acid and the.-

carbon tetrachlorid will be evaporated.

Another modification of the method of producing SeOUl directly in liquidform is as follows:

Mix SeO and a dehydrating agent, as for example, phosphorus pentoxid (P0 or calcium chlorid (CaOl heat the mixture and pass hydrochloric acidgas (HCl) over the heated mixture. The reaction may proceed inaccordance with the following equa tions:

(as SeO +2HCl:SeO .2HCl

The SeOCl may be distilled over and condensed and the metaphosphoricacid will remain as a residue.

The foregoing equations are satisfied by the following proportions, viz:

5e0 111 parts by Weight;

P 142 parts by Weight;

HCl, 73 parts by Weight.

lit may be necessary or desirable to moderate the solvent action ofselenium oxychlorid for certain purposes. This may be done, for example,by mixing with a quantity of the oxychlorid a quantity of some substanceWhich is not an active substance, and which will thus act as a diluent.For example, one may mix 25 pounds of selenium oxychlorid with 75 poundsof carbon tetrachlorid, thus producing a. mild form of solvent which maybe employed, in general, Where mild. solution. is desired as a solventor a reagent. The mixture of selenium oxychlorid with such a substancemay be made of any de sired. proportions, according to the use orpurpose intended. Crude selenium may be employed in the process; or, ifdesired, compounds of selenium, such as iron selenid (Feta'e) or copperselenid (CuSe) may be employed. F or example, Fecle may be suspended incarbon tetrachlorid and chlorin gas passed therethrough, producing SeCl. and FeCl or FeUl The Se Ol that is selenium monochlorid, may beconverted into selenium tetraohlorid by continuing the chlorinationprocess. The necessary proportion oi Water to convert the seleniumtetrachlorid to selenium oxychlorid may be added. Separation of thematerials may be effected in any suitable manner, it being understoodthat if the selenium oxychlorid be distilled, the Fe i or Fetll willremain as a residue. the water he added after the selenium tetrachloridhas been formed, the reaction may proceed. in accordance with thefollowing equations:

The foregoing detailed description has been given for clearness otunderstanding only and no unnecessary limitations should What I regardas new, and desire to secure by Letters Patent, 1s r 1 l. lhe process ofproducing selenium oxychlorld which consists in chemically cominning ina bath mgredients comprising selenium, chlorin and oxygen to form saiddioxid to form said selenium oxychlorid directly as a liquid andcontinuing such reaction in the presence as a solvent of thellClLlltl'SElQllllllTl oxychlorid formed.

The process of producing selenium oxychlorid which comprises chemicallycombining selenium tetrachlorid and selenium dioxid to form saidselenium oxychlorid directly as a liquid, continuing such reaction inthe presence as a solvent of the liquid selenium oxychlorid formed, andthen puri- Iying the product by distillation.

4. The process of producing selenium oxychlorid which compriseschemically combining selenium tetrachlorid and selenium dioxid in thepresence of a solvent for both constituent compounds.

5. The process of producing selenium oxychlorid which compriseschemically combining selenium tetrachlorid and selenium dioxid in thepresence of a solvent for both constituent compounds, and producing saidselenium oxychl'orid directly as a liquid.

6. The process of producing selenium oxychlorid which compriseschemically combining selenium tetrachlorid and selenium dioxid in thepresence of a solvent for selenium oxychlorid, thus producing SeOCl inliquid form, and continuing the reaction in the liquid bath as theselenium tetrachlorid and selenium. (lioxid are progressively dis solvedin the selenium oxychlorid formed.

7. The process of producing selenium 0xychlorid which compriseschemically combining selenium tetrachlorid and selenium dionid in thepresence of a solvent for selenium oxychlorid, thus producing Se OCl inliquid form, continuing the reaction. in the liquid bath as the seleniumtetrachlorid and selenium dioxid are progressively dissolved in theselenium oxychlorid formed, and distilling of? the solvent for seleniumoxychlorid.

8. The process of producing selenium oxychlorid which compriseschemically combining selenium tetra-chlorid andselenium dioxid in thepresence of a solvent for selenium oxychlorid, thus producing EieOCl inliquid form, continuing the reaction in the lie uid bath as the seleniumtetrachlorid and selenium dioxid are progressively dissolved in theselenium oxychlorid formed, distilling oil the solvent for seleniumoxychlorid, end then purifying the selenium oxychlorid by distillation.

9. The process of producin selenium oxy chlorid which comprises mixingselenium and a solvent for both chlorin and selenium monochlorid,introducing chlorin gas therein to convert the selenium to seleniummonochlorid and ultimately to selenium tetrachlorid, mixingseleniumdioxid with the liquid holding the selenium tetrachlorid insuspension and thus effecting the formation of selenium oxychlorid as aliquid, and distilling off said solvent.

10. The process of producing selenium..

oxychlorid which comprises mixing selenium and a. solvent for bothchlorin and selenium monochlorid, introducing chlorin gas therein tocomert the selenium to selenium monochlorid and ultimately to seleniumtetrachlorid, mixing selenium dioxid with the liquid holding theselenium tetrachlorid in suspension and thus elfecting the formation ofselenium oxychlorid as a liquid, distilling off said solvent, andpurifying the selenium oxychlorid by distillation.

11. The process of producing selenium oxychlorid which compriseschemically combining selenium tetrachlorid and selenium dioxid in thepresence of carbon tetrachlorid.

12. T he process of producing selenium oxychlorid which compriseschemically com bining ingredients comprising selenium, oxygen andchlorin in the presence of a solvent for selenium oxychlorid.

13. The process of producing selenium oxychlorid which compriseschemically combining ingredients comprising selenium,-

oxygen and chlorin in the presence of selenium oxychlorid and a solventfor the same.

14:. The steps for producing selenium tetrachlorid insuspensioncomprising: mixing selenium and a solvent for both chlorin and seleniummonochlorid; introducing chlorin gas into said mixture to form'seleniummonochlorid which acts as a solvent for selenium; and continuing theprocess until i the selenium and selenium monochlorid are converted intoselenium tetrachlorid.

15. The process of producing selenium oxychlorid which compriseschemically combining selenium dioxid, selenium and chlorin gas by achlorinating process.

VICTOR LENHER.

